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| United States Patent |
5,565,396
|
|
Frey
, et al.
|
October 15, 1996
|
Catalyst systems and polymerization processes
Abstract
In accordance with the present invention there is provided a
cyclopentadienyl-type ligand represented by the formula ZA, wherein Z is a
cyclopentadienyl-type group, wherein A is --YPR.sub.2, --YNR.sub.2, or
--NR.sub.2, wherein Y is an alkylene group containing 1 to 24 carbon
atoms, wherein each R is individually selected from alkyl groups
containing 1 to 20 carbon atoms. Another aspect of the invention is to
provide a metallocene represented by the formula ZAMX.sub.3, wherein Z and
A are as described above, M is a Group IVB or VB transition metal, and X
is a halide. Other aspects of the present invention include catalyst
systems comprising the metallocenes and an organoaluminoxane, processes
for preparing the above defined ligands, metallocenes and catalyst
systems, and polymerization processes employing the catalyst systems.
| Inventors:
|
Frey; Krisztina (Bayreuth, DE);
von Massow; Gabriele (Bayreuth, DE);
Alt; Helmut G. (Bayreuth, DE);
Welch; M. Bruce (Bartlesville, OK)
|
| Assignee:
|
Phillips Petroleum Company (Bartlesville, OK)
|
| Appl. No.:
|
444990 |
| Filed:
|
May 19, 1995 |
| Current U.S. Class: |
502/113; 502/117; 556/53 |
| Intern'l Class: |
C08F 004/62; C08F 004/64 |
| Field of Search: |
502/105,113,117
|
References Cited
U.S. Patent Documents
| 4173590 | Nov., 1979 | Schmidbauer | 260/606.
|
| 4701432 | Oct., 1987 | Welborn, Jr. | 502/115.
|
| 4837226 | Jun., 1989 | Coughenour et al. | 514/443.
|
| 5096867 | Mar., 1992 | Canich | 502/103.
|
| 5155080 | Oct., 1992 | Elder et al. | 505/152.
|
| 5191132 | Mar., 1993 | Patsidis et al. | 585/375.
|
| 5208357 | May., 1993 | Mintz | 556/43.
|
| 5227440 | Jul., 1993 | Canich et al. | 526/129.
|
| 5272236 | Dec., 1993 | Lai et al. | 526/348.
|
| 5349100 | Sep., 1994 | Mintz | 556/53.
|
| 5371256 | Dec., 1994 | Togni et al. | 556/14.
|
| 5399636 | Mar., 1995 | Alt et al. | 502/117.
|
Other References
"Reactions of [Diphenylphosphino)methyl]lithium with Dimethylfulvene",
Schore and Labelle, J. Org. Chem. 1981, 46, pp. 2306-2310.
"Indirect Metal-Metal Linkage: Cyclic Ferrocene Complexes with a Second
Metal Linked via Remote Phosphine Functionality", Schore et al., Inorg.
Chem. 1981, vol. 20, 3200-08.
Synthesis of [C.sub.5 (CH.sub.3)4H]CH.sub.2 CH.sub.2 CH.sub.2 P(C.sub.6
H.sub.5).sub.2 : "A Novel Heterodifunctional Ligand Possessing Both a
Tetramethylcyclopentadiene and a Remote Diphenylphosphine Functionality",
Bensley et al., J. Org. Chem. 1988, 53, pp. 4417-4419.
"New Heterodifunctional Ligands for Organotransition-Metal Chemistry:
Ph.sub.2 P(CH.sub.2).sub.n (c.sub.5 Me.sub.4 H(n=0,2)", Szymoniak et al.,
J. Org. Chem., 1990, 55, pp. 1429-1432.
"Synthesis of (C.sub.6 H.sub.5).sub.2 PCH.sub.2 Si(CH.sub.3).sub.2 C.sub.5
H.sub.4 Li: A novel heterodiifunctional System for the Directed Linkage of
Dissimilar Transition Metal Fragments", Schore, J. Am. Chem. Soc., 101,
7410-12, Nov. 21, 1979.
"Complexes Du Titane Et Du Zirconium Contenant Les Ligands
Cyclopentadienylphenylphosphine et cyclopentadienylethyldiphenylphosphine:
Access a des Structures Heterobimetallizues", LeBlank et al., J.
Organomet. Chem. 231, . . .
"Cyclic Conjugate 5-and 7-ring systems. I. Synthesis and reactions of
fulvenecarboxaldehydes", Kitsuta, Chem. Abstracts vol. 59, 2706-07, 1963.
"An Exceptionally Simple and Efficient Method for the Preparation of a Wide
Variety of Fulvenes", Stone et al., J. Org. Chem. vol. 49, No. 11, Jun.
1984.
Journal of Organometallic Chemistry, 456 (1993) 89-85, "Zirkonocenkomplexe
mit einem funktionalisierten Cyclopentadienylliganden. Molekulstruktur von
(.eta..sup.5 :.eta..sup.2 -C.sub.5 H.sub.4 CMe.sub.2 C.sub.9
H.sub.7)Zr)(PMe.sub.3)", Helmut G. Alt et al.
|
Primary Examiner: Caldarola; Glenn A.
Attorney, Agent or Firm: Corvin; Carl D.
Parent Case Text
This is a divisional of copending application Ser. No. 08/303,982, filed
Sep. 9, 1994.
Claims
That which is claimed is:
1. A catalyst system comprising a metallocene and a cocatalyst, wherein
said metallocene is represented by the formula ZAMX.sub.3 ;
wherein Z is a cyclopentadienyl-type group and is an unsubstituted
cyclopentadienyl, substituted cyclopentadienyl, unsubstituted indenyl,
substituted indenyl, unsubstituted fluorenyl, or substituted fluorenyl
group, wherein the substituents on said cyclopentadienyl-type group are
hydrocarbyl groups containing 1 to 12 carbon atoms, alkoxy groups
containing 1 to 12 carbon atoms, trialkylsilyl groups where each alkyl
contains 1 to 12 carbon atoms, alkyl halide groups where the alkyl group
contains 1 to 12 carbon atoms, or halide; and
wherein A is --YPR.sub.2 or --YNR.sub.2, wherein Y is an alkylene group
containing 1 to 24 carbon atoms, wherein each R is individually selected
from alkyl groups containing 1 to 20 carbon atoms;
wherein M is a Group IVB or VB transition metal;
wherein X is a halide; and
wherein said cocatalyst is an organoaluminoxane having repeating units of
the formula
##STR3##
wherein each R.sup.2 is a hydrocarbyl group containing 1-8 carbon atoms,
and x is 2 to 50.
2. A catalyst system consisting essentially of a metallocene and a
cocatalyst, wherein said metallocene is represented by the formula
ZAMX.sub.3 ;
wherein Z is a cyclopentadienyl-type group and is an unsubstituted
cyclopentadienyl, substituted cyclopentadienyl, unsubstituted indenyl,
substituted indenyl, unsubstituted fluorenyl, or substituted fluorenyl
group, wherein the substituents on said cyclopentadienyl-type group are
hydrocarbyl groups containing 1 to 12 carbon atoms, alkoxy groups
containing 1 to 12 carbon atoms, trialkylsilyl groups where each alkyl
group contains 1 to 12 carbon atoms, alkyl halide groups where the alkyl
group contains 1 to 12 carbon atoms, or halide;
wherein A is --YPR.sub.2 or --YNR.sub.2, wherein Y is an alkylene group
containing 1 to 24 carbon atoms, wherein each R is individually selected
from alkyl groups containing 1 to 20 carbon atoms;
wherein M is a Group IVB or VB transition metal;
wherein X is a halide; and
wherein said cocatalyst is an organoaluminoxane having repeating units of
the formula
##STR4##
wherein each R.sup.2 is a hydrocarbyl group containing 1-8 carbon atoms,
and x is 2 to 50.
3. A polymerization process comprising contacting under polymerization
conditions at least one olefin containing 2 to 18 carbon atoms and the
catalyst system of claim 1.
4. A process according to claim 3 where said polymerization conditions
include a temperature in the range of from about 20.degree. C. to about
300.degree. C.
5. A process according to claim 3 wherein said at least one olefin
comprises ethylene or propylene.
6. A catalyst system according to claim 1 wherein Y contains 1 to 20 carbon
atoms and wherein each R contains 1 to 10 carbon atoms.
7. A catalyst system according to claim 6 wherein Y contains 1 to 16 carbon
atoms and wherein each R contains 1 to 5 carbon atoms.
8. A catalyst system according to claim 7 wherein Y is an unsubstituted or
substituted methylene or ethylene group and wherein each R is methyl.
9. A catalyst system according to claim 8 wherein the substituents on said
cyclopentadienyl-type group are alkyl groups containing 1 to 10 carbon
atoms.
10. A catalyst system according to claim 9 wherein the substituents are
alkyl groups containing 1 to 6 carbon atoms.
11. A catalyst system according to claim 10 wherein A is --CH.sub.2
P(CH.sub.3).sub.2.
Description
The present invention relates to the preparation of heterodifunctional
cyclopentadienyl-type ligands and metallocenes.
BACKGROUND OF THE INVENTION
Cyclopentadienyl-type ligands have found a number of uses in the past. As
used herein, the term cyclopentadienyl-type ligands includes ligands
containing a cyclopentadienyl-type group. Cyclopentadienyl-type groups as
used herein a cyclopentadienyl functionality and include unsubstituted
cyclopentadienyl, substituted cyclopentadienyl, unsubstituted indenyl,
substituted indenyl, unsubstituted fluorenyl, and substituted fluorenyl
groups. Such ligands have utility in the preparation of metallocenes
useful for the polymerization of olefins.
Other applications for metallocenes include asymmetric hydrogenation,
alkene epoxidation, alkene isomerization, ketone reduction, and as
stoichiometric reagents for stereoselective cobalt-mediated reactions,
allyltitanium addition reactions with aldehydes, and the highly selective
formation of allylic amines.
It would therefore be desirable to produce a variety of novel ligands from
readily available materials employing a simple and economical process.
SUMMARY OF THE INVENTION
An object of the present invention is to provide an economical and simple
processes for preparing new cyclopentadienyl-type ligands.
Another object of the present invention is to provide a variety of
cyclopentadienyl-type ligands useful in preparing metallocenes.
Another object of the present invention is to provide various metallocenes
useful in the polymerization of olefins.
Another object of the present invention is to provide processes for
preparing new metallocenes.
Another object of the present invention is to provide catalyst systems
capable of polymerizing olefins.
Another object of the present invention is to provide processes for
preparing catalyst systems.
Another object of the present invention is to provide olefin polymerization
processes employing the catalyst systems.
In accordance with the present invention there is provided
cyclopentadienyl-type ligands represented by the formula ZA, wherein Z is
a cyclopentadienyl-type group and wherein A is --YPR.sub.2, --YNR.sub.2,
or --NR.sub.2 wherein Y is an alkenyl or substituted alkenyl group
containing 1 to 24 carbon atoms and wherein each R is individually
selected from alkyl groups containing 1 to 20 carbon atoms. Another aspect
of the invention is to provide metallocenes represented by the formula
ZAMX.sub.3, wherein Z and A are as described above, M is a Group IVB or VB
transition metal, and X is a halide. Other aspects of the present
invention include catalyst systems comprising the metallocenes and an
organoaluminoxane, processes for preparing the above defined ligands,
metallocenes and catalyst systems, and polymerization processes employing
the catalyst systems.
DETAILED DESCRIPTION OF THE INVENTION
The cyclopentadienyl-type ligands of the present invention are represented
by the formula ZA, wherein Z is a cyclopentadienyl-type group and A is
--YPR.sub.2, --YNR.sub.2, or --NR.sub.2, wherein Y is an alkylene group
containing 1 to 24 carbon atoms, wherein each R is individually selected
from alkyl groups containing 1 to 20 carbon atoms, preferably 1 to 10
carbon atoms, more preferably 1 to 5 carbon atoms, and most preferably the
R groups are methyl or ethyl. Preferably Y contains 1 to 20 carbon atoms,
more preferably 1 to 16 carbon atoms, and most preferably Y is an
unsubstituted or substituted methylene or ethylene group. Some examples of
Y include methylene, ethylene, dimethylmethylene, dimethylethylene,
phenylethylene, butylethylene, diphenylethylene, propylene, and butylene.
Some examples of R include methyl, ethyl, propyl, isopropyl, butyl,
tert-butyl, isobutyl, amyl, isoamyl, hexyl, cyclohexyl, heptyl, octyl,
nonyl, decyl, cetyl, 2-ethylhexyl. Excellent results have been obtained
when R is methyl and those compounds are preferred. In the following
examples Me is methyl, Et is ethyl, Ph is phenyl, and t-Bu is tert-butyl.
Typical examples of A include --CH.sub.2 PMe.sub.2, --CH.sub.2 CH.sub.2
PMe.sub.2, --CMe.sub.2 PMe.sub.2, --CMe.sub.2 CH.sub.2 PMe.sub.2,
--CPhHCH.sub.2 PMe.sub.2, --CPh.sub.2 CH.sub.2 PMe.sub.2,
--C(t-Bu)HCH.sub.2 PMe.sub.2, --CH.sub.2 PMe.sub.2, --CH.sub.2 CH.sub.2
PMe.sub.2, --CMe.sub.2 PMe.sub.2, --CMe.sub.2 CH.sub.2 PMe.sub.2,
--CPhHCH.sub.2 PMe.sub.2, --CPh.sub.2 CH.sub.2 PMe.sub.2,
--C(t-Bu)HCH.sub.2 PMe.sub.2, --CH.sub.2 PEt.sub.2, --CH.sub.2 CH.sub.2
PEt.sub.2, --CME.sub.2 PEt.sub.2, --CMe.sub.2 CH.sub.2 PEt.sub.2,
--CPhHCH.sub.2 PEt.sub.2,--CPh.sub.2 CH.sub.2 PEt.sub.2, --CMe.sub.2
PEt.sub.2, --CH.sub.2 PEt.sub.2, --CH.sub.2 CH.sub.2 PEt.sub.2,
--CMe.sub.2 PEt.sub.2, --CMe.sub.2 CH.sub.2 PEt.sub.2, --CPhHCH.sub.2
PEt.sub.2, --CPh.sub.2 CH.sub.2 PEt.sub.2, --C(t-Bu)HCH.sub.2 PEt.sub.2,
--CH.sub.2 NMe.sub.2, --CH.sub.2 CH.sub.2 NMe.sub.2, --CMe.sub.2
NMe.sub.2, --CMe.sub.2 CH.sub.2 NMe.sub.2, --CPhHCH.sub.2 NMe.sub.2,
--CPh.sub.2 CH.sub.2 NMe.sub.2, --C(t-Bu)HCH.sub.2 NMe.sub.2, --CH.sub.2
NMe.sub.2, --CH.sub.2 CH.sub.2 NMe.sub.2, --CMe.sub.2 NMe.sub.2,
--CMe.sub.2 CH.sub.2 NMe.sub.2, --CPhHCH.sub.2 NMe.sub.2, --CPh.sub.2
CH.sub.2 NMe.sub.2, --C(t-Bu)HCH.sub.2 NMe.sub.2, --CH.sub.2 NEt.sub.2,
--CH.sub.2 CH.sub.2 NEt.sub.2, --CMe.sub.2 NEt.sub.2, --CMe.sub.2 CH.sub.2
NEt.sub.2, --CPhHCH.sub.2 NEt.sub.2, --CPh.sub.2 CH.sub.2 NEt.sub.2,
--C(t-Bu)HCH.sub.2 NEt.sub.2, --CH.sub.2 NEt.sub.2, --CH.sub.2 CH.sub.2
NEt.sub.2, --CMe.sub.2 NEt.sub.2, --CMe.sub.2 CH.sub.2 NEt.sub.2,
--CPhHCH.sub.2 NEt.sub.2, --CPh.sub.2 CH.sub.2 NEt.sub.2,
--C(t-Bu)HCH.sub.2 NEt.sub.2, --NMe.sub.2, and --NEt.sub.2.
As noted above, cyclopentadienyl-type group as used herein is a group
containing a cyclopentadienyl functionality and is an unsubstituted
cyclopentadienyl, substituted cyclopentadienyl, unsubstituted indenyl,
substituted indenyl, unsubstituted fluorenyl, or substituted fluorenyl
group. The substituents on the cylcopentadienyl-type group can include
hydrocarbyl groups containing 1 to 12 carbon atoms, alkoxy groups
containing 1 to 12 carbon atoms, trialkylsilyl groups where each alkyl
contains 1 to 12 carbon atoms, alkyl halide groups where the alkyl
contains 1 to 12 carbon atoms, or halide. Preferably the substituents
containing alkyl groups contain 1 to 10 carbon atoms, more preferably 1 to
6 carbon atoms. Some examples of substituents include methyl, ethyl,
propyl, butyl, tert-butyl, isobutyl, amyl, isoamyl, hexyl, cyclohexyl,
heptyl, octyl, nonyl, decyl, dodecyl, 2-ethylhexyl, pentenyl, butenyl,
phenyl, chloride, bromide, and iodide.
Examples of typical cyclopentadienyl-type ligands include
[1-phenyl-2-(dimethylphosphino)ethyl]cyclopentadiene,
[1,1-dimethyl-2-(dimethylphosphino)ethyl]cyclopentadiene,
[1,1-diphenyl-2-(dimethylphosphino_ethyl]cyclopentadiene,
[1-methyl-1-phenyl-2-(dimethylphosphino)ethyl]cyclopentadiene,
[1-tert-butyl-2-(dimethylphosphino)ethyl]cyclopentadiene,
[1-phenyl-2-(dimethylphosphino)ethyl]indene,
[1,1-dimethyl-2-(dimethylphosphino)ethyl]indene,
[1,1-diphenyl-2-(dimethylphosphino)ethyl]indene,
[1-methyl-1-phenyl-2-(dimethylphosphino)ethyl]indene,
[1-tert-butyl-2-(dimethylphosphino)ethyl]indene,
9-(trimethylsilyl)-2-(1-(2-dimethylphosphino)ethyl)fluorene,
9-(1-(2-dimethylphosphino)ethyl)fluorene,
[(dimethylamino)methyl)]cyclopentadiene,
[(diethylamino)methyl)]cyclopentadiene,
[(dimethylamino)(methyl)(phenyl)methyl)]cyclopentadiene,
[(diethylamino)(methyl)(phenyl)methyl)]cyclopentadiene,
[(dimethylamino)(phenyl)methyl)]cyclopentadiene,
[(diethylamino)(phenyl)methyl)]cyclopentadiene,
[1-phenyl-2-(diethylamino)ethyl]cyclopentadiene,
[1-phenyl-2-(dimethylamino)ethyl)cyclopentadiene,
[1-phenyl-2-(dimethylamino)ethyl)cyclopentadiene,
[1,1-dimethyl-2-(dimethylamino)ethyl]cyclopentadiene,
[1,1-diphenyl-2-(dimethylamino)ethyl]cyclopentadiene,
[1-methyl-1-phenyl-2-(dimethylamino)ethyl]cyclopentadiene,
[1-tert-butyl-2-(dimethylamino)ethyl]cyclopentadiene,
[1-phenyl-2-(dimethylamino)ethyl]indene,
[1,1-dimethyl-2-(dimethylamino)ethyl]indene,
[1,1-diphenyl-2-(dimethylamino)ethyl]indene,
[1-methyl-1-phenyl-2-(dimethylamino)ethyl]indene,
[1-tert-butyl-2-(dimethylamino)ethyl]indene,
9-(dimethylamino)methyl)fluorene, 9-(1-(2-dimethylamino)ethyl)fluorene,
9-(trimethylsilyl)-9-(dimethylamino)methyl)fluorene, and
9-(trimethylsilyl)-9-(1-(2-dimethylamino)ethyl)fluorene.
One method for preparing the cyclopentadienyl-type ligands, Method I,
involves reacting fulvene compounds with a nucleophile, wherein the
nucleophile is represented by the formula JA, wherein J is an alkali
metal, preferably lithium, and wherein A is as described above.
The fulvene compound is represented by the general formula
##STR1##
wherein each R' and R" is individually selected from the group consisting
of alkyl, aryl, alkenyl, and alkoxy groups containing 1 to 20 carbon
atoms, preferably 1 to 10 carbon atoms, halogen, and hydrogen; and wherein
n is 1 to 4. Some examples of R' and R" include methyl, ethyl, propyl,
isopropyl, butyl, tert-butyl, isobutyl, tert-butyl, amyl, isoamyl, hexyl,
cyclohexyl, heptyl, octyl, nonyl, decyl, cetyl, 2-ethylhexyl, phenyl, and
phenylmethyl.
Examples of typical fulvene compounds include 6-methylfulvene,
6-ethylfulvene, 6-isopropylfulvene, 6-butylfulvene, 6-tert-butylfulvene,
6-octylfulvene, 1,6-dimethylfulvene, 1,2,6-trimethylfulvene,
1,2,3,6-tetramethylfulvene,1,2,3,4,6-pentamethylfulvene.6,6-dimethylfulven
e, 3,6,6-trimethylfulvene, 6,6-diethylfulvene, 6,6-diphenylfulvene,
6-ethyl-6-ethylfulvene, 6-isopropyl-6-methylfulvene, 6,6-dibutylfulvene,
6,6-dioctylfulvene, 6-methyl-6-octylfulvene, 6-methyl-6-phenyl,
1,6,6-trimethylfulvene, 1,2,6,6-tetramethylfulvene,
1,2,3,6,6-pentamethylfulvene, and 1,2,3,4,6,6-hexamethylfulvene. Of the
fulvene compounds, 6-methylfulvene, 6-phenylfulvene, 6-methyl-6-phenyl,
6-tert-butylfulvene, 6,6-dimethylfulvene, and 6,6-diphenylfulvene are
preferred because they produce excellent results and are readily
available.
The fulvene compounds can be prepared by any method known in the art. One
such method is disclosed in J. Org. Chem., Vol. 49, No. 11, pp. 1849-53
1984, the disclosure of which is incorporated herein by reference. Many
such compounds are commercially available.
When reacting the fulvene compound and the nucleophile in Method I,
generally the nucleophile compound will be present in an amount in the
range of from about 0.1 mole to about 20 moles per mole of fulvene
compound, preferably from 0.2 mole to about 10 moles per mole, and more
preferably from 0.5 mole to 5 moles per mole of fulvene compound.
The reaction conditions for reacting the fulvene compound and the
nucleophile in Method I are generally in the range of from about
-100.degree. C. to about 150.degree. C., preferably from about
-100.degree. C. to about 125.degree. C., and more preferably from
-100.degree. C. to about 100.degree. C.
Generally a diluent is employed in Method I when reacting the fulvene
compound and the nucleophile. Typical diluents include polar diluents such
as for example tetrahydrofuran, or nonpolar diluents such as alkanes,
cycloalkanes, aromatic hydrocarbons, and non-cyclic ethers. Some specific
examples include toluene, heptane, hexane, and diethylether.
Another method for preparing the inventive cyclopentadienyl-type ligands,
Method II, involves reacting a halocyclopentadienyl-type compound and the
nucleophile JA, described above, wherein the halocyclopentadienyl-type
compound is represented by the formula ZCH.sub.2 X' wherein Z is a
cyclopentadienyl-type group as described above and X' is a halide,
preferably bromine or chlorine. The method has been found useful in
preparing cyclopentadienyl-type ligands containing an unsubstituted or
substituted fluorenyl group.
When reacting the halocyclopentadienyl-type compound and the nucleophile in
Method II, generally the nucleophile compound will be present in an amount
in the range of from about 0.1 mole to about 20 moles per mole of
halocyclopentadienyl-type compound, preferably from 0.2 mole to about 10
moles per mole, and more preferably from 0.5 mole to 5 moles per mole of
halocyclopentadienyl-type compound.
The reaction conditions for reacting the fulvene compound and the
nucleophile in Method II are generally in the range of from about
-100.degree. C. to about 150.degree. C., preferably from about
-100.degree. C. to about 125.degree. C., and more preferably from
-100.degree. C. to about 100.degree. C.
Generally a diluent is employed in Method II when reacting the
halocyclopentadienyl-type compound and the nucleophile. Typical diluents
include those described above, such as polar diluents such as for example
tetrahydrofuran, or nonpolar diluents such as alkanes, cycloalkanes,
aromatic hydrocarbons, and non-cyclic ethers. Some specific examples
include toluene, heptane, hexane, and diethylether. Good results have been
obtained with tetrahydrofuran and it is preferred.
Another method for preparing the inventive cyclopentadienyl-type ligands,
Method III, involves (1) reacting a halosilane with an alkali metal salt
of a cyclopentadienyl-type compound to form a silylcyclopentadienyl-type
compound, (2) reacting the silylcyclopentadienyl-type compound with an
alkali metal alkyl and methylene dichloride, to produce a chloromethylated
silylcyclopentadienyl-type compound, and then (3) reacting the
chloromethylated silylcyclopentadienyl-type compound with the above
defined nucleophile, JA, to produce the cyclopentadienyl-type ligand. This
method has been found especially useful in preparing cyclopentadienyl-type
ligands containing a fluorenyl group. Silylfluorene compounds can be
prepared by any method known such as disclosed in J. Am. Chem. Soc. 72
(1950) 1688, H. Gilman et al. the disclosure of which is herein
incorporated by reference.
The halosilane compound employed in Method III is represented by the
formula X"Si(R.sup.1).sub.3, wherein X" is a halide and wherein each
R.sup.1 is individually an alkyl group or hydrogen, wherein the alkyl
group contains 1 to 20 carbon atoms, preferably 1 to 10, and more
preferably 1 to 5 carbon atoms. Typical examples of R.sup.1 include
methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, amyl,
isoamyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, cetyl,
2-ethylhexyl. Excellent results have been obtained with
chlorotrimethylsilane and it is preferred.
Typically the alkali metal salts of cyclopentadienyl-type compounds
employed in Method III can be prepared by dissolving a
cyclopentadienyl-type compound in a suitable liquid diluent and then
adding an alkali metal compound, such as an alkali metal alkyl. Techniques
of forming such salts are known in the art. The alkali metal alkyls
employed in preparing the alkali metal salt of the cyclopentadienyl-type
compound can include any alkali metal alkyls capable of forming a suitable
alkali metal salt. Typically the alkali metal alkyls would be selected
from the alkyls of sodium, potassium, and lithium and the alkyl group
would have 1 to 8, preferably 1 to 6 carbon atoms. The preferred alkali
metal alkyls are lithium alkyls. Due to availability and efficacy,
butyllithium is especially preferred. In preparing the alkali metal salt
of the cyclopentadienyl-type compound, the amount of alkali metal alkyl
employed is generally in the range of from about 0.5 mole to about 50
moles per mole of cyclopentadienyl-type compound, preferably 0.5 mole to
20 moles per mole of cyclopentadienyl-type compound.
When reacting the halosilane and the alkali metal salt of the
cyclopentadienyl-type compound in step (1) of Method III, the halosilane
is generally present in an amount in the range of from about 0.1 mole to
about 20 moles per mole of cyclopentadienyl-type compound, preferably from
0.2 mole to about 10 moles per mole, and more preferably from 0.5 mole to
5 moles per mole of cyclopentadienyl-type compound.
When reacting the silylcyclopentadienyl-type compound, the alkali metal
alkyl, and methylene dichloride in step of (2) Method III, the alkali
metal alkyl and methylene dichloride are generally each present in an
amount in the range of from about 0.1 mole to about 20 moles per mole of
silylcyclopentadienyl-type compound, preferably from 0.2 mole to about 10
moles per mole, and more preferably from 0.5 mole to 5 moles per mole of
silylcyclopentadienyl-type compound.
When reacting the chloromethylated silylcyclopentadienyl-type compound and
the nucleophile in step (3) of Method III, the nucleophile is generally
present in an amount in the range of from about 0.1 mole to about 20 moles
per mole of chloromethylated silylcyclopentadienyl-type compound,
preferably from 0.2 mole to about 10 moles per mole, and more preferably
from 0.5 mole to 5 moles per mole of chloromethylated
silylcyclopentadienyl-type compound.
Generally a diluent is employed when conducting the above described steps
of Method III. Typical diluents include those described above such as for
example polar diluents such as tetrahydrofuran, or nonpolar diluents such
as alkanes, cycloalkanes, aromatic hydrocarbons, and non-cyclic ethers.
Some specific examples include benzene, toluene, heptane, hexane,
cyclohexane, and diethylether.
The reaction temperatures in steps (1),(2), and (3) of Method III are
generally in the range of from about -100.degree. C. to about 150.degree.
C., preferably from about -100.degree. C. to about 125.degree. C., and
more preferably from -100.degree. C. to about 100.degree. C.
The inventive metallocenes are transition metal-containing trihalo
complexes represented by the formula ZAMX.sub.3 wherein Z is a
cyclopentadienyl-type group as described above, A is as described above, M
is a Group IVB or VB transition metal, preferably titanium, zirconium,
hafnium or vanadium, more preferably zirconium or titanium, most
preferably zirconium, and X is a halide, preferably X is chlorine.
The metallocenes are prepared by reacting an alkali metal alkyl as
described above, the cyclopentadienyl-type ligand, and a metal halide
compound represented by the formula MX.sub.4, wherein M is a transition
metal as described above, and X is a halide.
Examples of suitable metal halides include titanium tetrachloride, titanium
tetraiodide, titanium tetrabromide, zirconium tetrachloride, zirconium
tetraiodide, zirconium tetrabromide, hafnium tetrachloride, hafnium
tetraiodide, hafnium tetrabromide, vanadium tetrachloride, vanadium
tetraiodide, vanadium tetrabromide, and mixtures thereof. Excellent
results have been obtained with titanium tetrachloride and zirconium
tetrachloride and they are preferred.
The alkali metal alkyl is selected from the alkyls of sodium, potassium,
and lithium and the alkyl group would have 1 to 8, preferably 1 to 6
carbon atoms. The preferred alkali metal alkyls are lithium alkyls. Due to
availability and efficacy, butyllithium is especially preferred.
The relative amounts of the alkali metal alkyl, the cyclopentadienyl-type
ligand, and the metal halide can vary broadly depending on the particular
compounds employed. Generally the alkali metal alkyl is present in an
amount in the range of from about 0.5 mole to about 2.0 moles per mole of
cyclopentadienyl-type ligand, preferably in the range of from 0.5 mole to
1.75 moles, and more preferably from 0.5 mole to 1.5 moles per mole of
cyclopentadienyl-type ligand. Generally the metal halide will be present
in an amount in the range of from about 0.1 mole to about 50 moles per
mole of cyclopentadienyl-type ligand, preferably in the range of from 0.2
mole to 20 moles, and more preferably from 0.5 mole to 10 moles per mole
of cyclopentadienyl-type ligand.
Generally a diluent is employed when reacting the alkali metal alkyl, the
cyclopentadienyl-type ligand, and the metal halide to form the
metallocene. Typical diluents include polar diluents such as for example
tetrahydrofuran, or nonpolar diluents such as alkanes, cycloalkanes,
aromatic hydrocarbons, and non-cyclic ethers. Some specific examples
include benzene, toluene, heptane, cyclohexane, hexane, and diethylether.
The temperature for reacting the alkali metal alkyl, the
cyclopentadienyl-type ligand, and the metal halide is generally in the
range of from about -100.degree. C. to about 100.degree. C., preferably
from about -100.degree. C. to about 80.degree. C., and more preferably
from -100.degree. C. to 60.degree. C. Although the alkali metal alkyl, the
cyclopentadienyl-type ligand, and the metal halide can be added in any
order, it is preferred to first react the alkali metal alkyl with the
cyclopentadienyl-type ligand to produce an alkali metal salt of the
cyclopentadienyl-type ligand, and then react the alkali metal salt of the
cyclopentadienyl-type ligand with the metal halide.
Typical examples of the inventive metallocenes include
[1-methyl-2-(dimethylylphosphino)ethyl]cyclopentadienylzirconium
trichloride,
[1-phenyl-2-(dimethylphosphino)ethyl]cyclopentadienylzirconium trichloride,
[1,1-dimethyl-2-(dimethylphosphino)ethyl]cyclopentadienylzirconium
trichloride,
[1,1-diphenyl-2-(dimethylphosphino)ethyl]cyclopentadienylzirconium
trichloride,
1-methyl-1-phenyl-2-(dimethylphosphino_ethyl]cyclopentadienylzirconium
trichloride,
[1-tert-butyl-2-(dimethylphosphino)ethyl]cyclopentadienylzirconium
trichloride,
[1-methyl-2-(dimethylphosphino)ethyl]cyclopentadienylzirconium tribromide,
[1-phenyl-2-(dimethylphosphino)ethyl]cyclopentadienylzirconium tribromide,
[1,1-dimethyl-2-(dimethylphosphino)ethyl]cyclopentadienylzirconium
tribromide,
[1,1-diphenyl-2-(dimethylphosphino)ethyl]cyclopentadienylzirconium
tribromide,
[1-methyl-1-phenyl-2-(dimethylphosphino)ethyl]cyclopentadienylzirconium
tribromide,
[1-tert-butyl-2-(dimethylphosphino)ethyl]cyclopentadienylzirconium
tribromide,
[1-phenyl-2-(dimethylphosphino)ethyl]indenylzirconium trichloride,
[1,1-dimethyl-2-(dimethylphosphino)ethyl]indenylzirconium trichloride,
[1,1-diphenyl-2-(dimethylphosphino)ethyl]indenylzirconium trichloride,
[1-methyl-1-phenyl-2-(dimethylphosphino)ethyl]indenylzirconium trichloride,
[1-tert-butyl-2-(dimethylphosphino)ethyl]indenylzirconium trichloride,
9-(1-(2-dimethylphosphino)ethyl)fluorenylzirconium trichloride,
](dimethylamino)methyl)]cyclopentadienylzirconium trichloride,
[(diethylamino)methyl)]cyclopentadienylzirconium trichloride,
[(dimethylamino)(phenyl)methyl)]cyclopentadienylzirconium trichloride,
[(diethylamino)(phenyl)methyl)]cyclopentadienylzirconium trichloride,
[(dimethylamino)(methyl)(phenyl)methyl)]cyclopentadienylzirconium
trichloride,
[(diethylamino)(methyl)(phenyl)methyl)]cyclopentadienylzirconium
trichloride,
[1-phenyl-2-(dimethylamino)ethyl]cyclopentadienylzirconium trichloride,
[1-phenyl-2-(diethylamino)ethyl)cyclopentadienylzirconium trichloride,
[1-phenyl-2-(dimethylamino)ethyl]indenylzirconium trichloride,
[1,1-dimethyl-2-(dimethylamino)ethyl]indenylzirconium trichloride,
[1,1-diphenyl-2-(dimethylamino)ethyl]indenylzirconium trichloride,
[1-methyl-1-phenyl-2-(dimethylamino)ethyl]indenylzirconium trichloride,
[1-tert-butyl-2-(dimethylamino)ethyl]indenylzirconium trichloride,
9-(1-(2-dimethylamino)ethyl)fluorenylzirconium trichloride,
[1-methyl-2-(dimethylphosphino)ethyl]cyclopentadienyltitanium trichloride,
[1-phenyl-2-(dimethylphosphino)ethyl]cyclopentadienyltitanium trichloride,
1,1-dimethyl-2-(dimethylphosphino)ethyl]cyclopentadienyltitanium
trichloride,
[1,1-diphenyl-2-(dimethylphosphino)ethyl]cyclopentadienyltitanium
trichloride,
[1-methyl-1-phenyl-2-(dimethylphosphino)ethyl]cyclopentadienyltitanium
trichloride,
[1-tert-butyl-2-(dimethylphosphino)ethyl]cyclopentadienyltitanium
trichloride,
1-phenyl-2-(dimethylphosphino)ethyl]indenyltitanium trichloride,
[1,1-dimethyl-2-(dimethylphosphino)ethyl]indenyltitanium trichloride,
[1,1-diphenyl-2-(dimethylphosphino)ethyl]indenyltitanium trichloride,
[1-methyl-1-phenyl-2-(dimethylphosphino)ethyl]indenyltitanium trichloride,
[1-tert-butyl-2-(dimethylphosphino)ethyl]indenyltitanium trichloride,
9-(1-(2-dimethylphosphino)ethyl)fluorenyltitanium trichloride,
[(dimethylamino)methyl)]cyclopentadienyltitanium trichloride,
[(diethylamino)methyl)]cyclopentadienyltitanium trichloride,
[(dimethylamino)(phenyl)methyl)]cyclopentadienyltitanium trichloride,
[(diethylamino)(phenyl)methyl)]cyclopentadienyltitanium trichloride,
[(dimethylamino)(methyl)(phenyl)methyl)]cyclopentadienyltitanium
trichloride,
[(diethylamino)(methyl)(phenyl)methyl)]cyclopentadienyltitanium
trichloride,
[1-phenyl-2-(diethylamino)ethyl]cyclopentadienyltitanium trichloride,
[1-phenyl-2-(dimethylamino)ethyl)cyclopentadienyltitanium trichloride,
[1-phenyl-2-(dimethylamino)ethyl]indenyltitanium trichloride,
[1,1-dimethyl-2-(dimethylamino)ethyl]indenyltitanium trichloride,
[1,1-diphenyl-2-(dimethylamino)ethyl]indenyltitanium trichloride,
[1-methyl-1-phenyl-2-(dimethylamino)ethyl]indenyltitanium trichloride,
[1-tert-butyl-2-(dimethylamino)ethyl)indenyltitanium trichloride,
9-(1-(2-dimethylamino)ethyl)fluorenyltitanium trichloride,
[1-methyl-2-(dimethylphosphino)ethyl]cyclopentadienylvanadium trichloride,
[1-phenyl-2-(dimethylphosphino)ethyl]cyclopentadienylvanadium trichloride,
[1,1-dimethyl-2-(dimethylphosphino)ethyl]cyclopentadienylvanadium
trichloride,
[1,1-diphenyl-2-(dimethylphosphino)ethyl]cyclopentadienylvanadium
trichloride,
[1-methyl-1-phenyl-2-(dimethylphosphino)ethyl]cyclopentadienylvanadium
trichloride,
[1-tert-butyl-2-(dimethylphosphino)ethyl]cyclopentadienylvanadium
trichloride,
[1-phenyl-2-(dimethylphosphino)ethyl]indenylvanadium trichloride,
[1.1-dimethyl-2-(dimethylphosphino)ethyl]indenylvanadium trichloride,
[1,1-diphenyl-2-(dimethylphosphino)ethyl]indenylvanadium trichloride,
[1-methyl-1-phenyl-2-(dimethylphosphino)ethyl]indenylvanadium trichloride,
[1-tert-butyl-2-(dimethylphosphino)ethyl]indenylvanadium trichloride,
9-(1-(2-dimethylphospino)ethyl)fluorenylvanadium trichloride,
[(dimethylamino)methyl)]cyclopentadienylvanadium trichloride,
[(diethylamino)methyl)]cyclopentadienylvanadium trichloride,
[(dimethylamino)(phenyl)methyl)]cyclopentadienylvanadium trichloride,
[(diethylamino)(phenyl)methyl)]cyclopentadienylvanadium trichloride,
[(dimethylamino)(methyl(pheynl)methyl)]cyclopentadienylvanadium
trichloride,
[(diethylamino)(methyl)(phenyl)methyl)]cyclopentadienylvanadium
trichloride,
[1-phenyl-2-(diethylamino)ethyl]cyclopentadienylvanadium trichloride,
[1-phenyl-2-(dimethylamino)ethyl)cyclopentadienylvanadium trichloride,
[1-phenyl-2-(dimethyloamino)ethyl]indenylvanadium trichloride,
[1,1-dimethyl-2-(dimethylamino)ethyl]indenylvanadium trichloride,
[1,1-diphenyl-2-(dimethylamino)ethyl]indenylvanadium trichloride,
1-methyl-1-phenyl-2-(dimethylamino)ethyl]indenylvanadium trichloride,
[1-tert-butyl-2-(dimethylamino)ethyl]indenylvanadium trichloride,
9-(1-(2-dimethylamino)ethyl)fluorenylvanadium trichloride,
[1-methyl-2-(dimethylphosphino)ethyl]cyclopentadienylhafnium trichloride,
[1-phenyl-2-(dimethylphosphino)ethyl]cyclopentadienylhafnium trichloride,
[1,1-dimethyl-2-(dimethylphosphino)ethyl]cyclopentadienylhafnium
trichloride,
[1,1-diphenyl-2-(dimethylphosphino)ethyl]cyclopentadienylhafnium
trichloride,
[1-methyl-1-phenyl-2-(dimethylphosphino)ethyl]cyclopentadienylhafnium
trichloride,
[1-tert-butyl-2-(dimethylphosphino)ethyl]cyclopentadienylhafnium
trichloride,
[1-phenyl-2-(dimethylphosphino)ethyl]indenylhafnium trichloride,
[1,1-dimethyl-2-(dimethylphosphino)ethyl]indenylhafnium trichloride,
[1,1-diphenyl-2-(dimethylphosphino)ethyl]indenylhafnium trichloride,
[1-methyl-1-phenyl-2-(dimethylphosphino)ethyl]indenylhafnium trichloride,
[1-tert-butyl-2-(dimethylphosphino)ethyl]indenylhafnium trichloride,
9-(1-(2-dimethylphosphino)ethyl)fluorenylhafnium trichloride,
[(dimethylamino)methyl)]cyclopentadienylhafnium trichloride,
[(diethylamino)methyl)]cyclopentadienylhafnium trichloride,
[(dimethylamino)(phenyl)methyl)]cyclopentadienylhafnium trichloride,
[(diethylamino)(phenyl)methyl)]cyclopentadienylhafnium trichloride,
[(dimethylamino)(methyl)(phenyl)methyl)]cyclopentadienylhafnium
trichloride,
[(diethylamino)(methyl)(phenyl)methyl)]cyclopentadienylhafnium trichloride,
[1-phenyl-2-(diethylamino)ethyl]cyclopentadienylhafnium trichloride,
[1-phenyl-2-(dimethylamino)ethyl)cyclopentadienylhafnium trichloride,
[1-phenyl-2-(dimethylamino)ethyl]indenylhafnium trichloride,
[1,1-dimethyl-2-(dimethylamino)ethyl]indenylhafnium trichloride,
[1,1-diphenyl-2-(dimethylamino)ethyl]indenylhafnium trichloride,
[1-methyl-1-phenyl-2-(dimethylamino)ethyl]indenylhafnium trichloride,
[1-tert-butyl-2-(dimethylamino)ethyl]indenylhafnium trichloride, and
9-(1-(2-dimethylamino)ethyl)fluorenylhafnium trichloride.
The metallocenes can be used in combination with a suitable cocatalyst to
produce catalyst systems for the polymerization of olefins. Examples of
suitable cocatalysts include any of those organometallic cocatalysts which
have in the past been employed in conjunction with transition
metal-containing olefin polymerization catalysts. Some typical examples
include organometallic compounds of metals of Groups IA, IIA, and IIIB of
the Periodic Table. Examples of such compounds include organometallic
halide compounds, organometallic hydrides, and metal hydrides. Some
specific examples include triethylaluminum, tri-isobutylaluminum,
diethylaluminum chloride, diethylaluminum hydride, and the like. Other
examples of known cocatalysts include the use of a stable non-coordinating
counter anion such as disclosed in U.S. Pat. No. 5,155,080, e.g. using
triphenyl carbenium tetrakis(pentafluorophenyl)boronate. Another example
would be the use of a mixture of trimethylaluminum and
dimethylfluoroaluminum such as disclosed by Zambelli et, Macromolecules,
22, 2186 (1989).
Currently, organoaluminoxane cocatalysts are the preferred cocatalysts.
Various techniques are known for making organoaluminoxanes. One technique
involves the controlled addition of water to a trialkylaluminum. Another
technique involves combining a trialkylaluminum and a hydrocarbon with a
compound containing water of adsorption or a salt containing water of
crystallization. Many suitable organoaluminoxanes are commercially
available.
Typically the organoaluminoxanes comprise oligomeric, linear and/or cyclic
hydrocarbyl aluminoxanes having repeating units of the formula
##STR2##
wherein each R.sup.2 is a hydrocarbyl group, preferably an alkyl group
containing 1-8 carbon atoms, x is 2 to 50, preferably 4 to 40, and more
preferably 10 to 40. Typically R.sup.2 is predominantly methyl or ethyl.
Preferably at least about 30 mole percent of the repeating groups have an
R.sup.2 which is methyl, more preferably at least 50 mole percent, and
still more preferably at least 70 mole percent. Generally in the
preparation of an organoaluminoxane, a mixture of linear and cyclic
compounds is obtained. Organoaluminoxanes are commercially available in
the form of hydrocarbon solutions, generally aromatic hydrocarbon
solutions.
A solid organoaluminoxy product can be prepared by reacting an
organoaluminoxane and an oxygen-containing compound selected from the
group consisting of organo boroxines, organic boranes, organic peroxides,
alkylene oxides, and organic carbonates.
The amount of organoaluminoxane relative to the metallocene can vary
broadly depending upon the particular catalyst selected and the results
desired. Typically, the organoaluminoxane is present in the amount of
about 0.5 moles to about 10,000 moles aluminum per mole of metal in the
metallocene, preferably about 10 moles to about 5,000 moles, and more
preferably 50 moles to 5,000 moles.
The above described steps for preparing ;the catalyst system are generally
conducted in the presence of a solvent or a diluent. Typical solvents or
diluents include for example tetrahydrofuran, heptane, hexane,
cyclohexane, benzene, toluene, and diethylether.
A variety of olefin compounds are suitable for use as monomers in the
polymerization process of the present invention. Olefins which can be
employed include linear, branched, and cyclic aliphatic olefins. While the
invention would appear to be suitable for use with any aliphatic olefin
known to be employed with metallocenes, those olefins having 2 to 18
carbon atoms are most often used. Ethylene and propylene are especially
preferred Often a second olefin (comonomer) having from 2 to 12 carbon
atoms, preferably from 4 to 10 carbon atoms can be employed. Typical
comonomers include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene,
2-pentene, 1-hexane, 2-hexene, cyclohexene, 1-heptene, and dienes such as
butadiene.
The polymerization processes according to the present invention can be
performed either batchwise or continuously. The olefin, metallocene, and
organoaluminoxane cocatalyst can be contacted in any order. It is
preferred that the metallocene and the organoaluminoxane are contacted
prior to contacting with the olefin. Generally a diluent such as isobutane
is added to the reactor. The reactor is heated to the desired reaction
temperature and olefin, such as ethylene, is then admitted and maintained
at a partial pressure within a range of from about 0.5 MPa to about 5.0
MPa (70-725 psi) for best results. At the end of the designated reaction
period, the polymerization reaction is terminated and the unreacted olefin
and diluent vented. The reactor can be opened and the polymer can be
collected as a free-flowing white solid and dried to obtain the product.
The reaction conditions for contacting the olefin and the catalyst system
can vary broadly depending on the olefin employed, and are those
sufficient to polymerize the olefins. Generally the temperature is in the
range of about 20.degree. C. to about 300.degree. C., preferably in the
range of 50.degree. C. to 150.degree. C. The pressure is generally in the
range of from about 0.5 MPa to about 5.0 MPa (70-725 psi).
The present invention can be employed in any olefin polymerization process
known such as gas phase particle form, slurry type, or solution phase
polymerizations. A preferred type particle from polymerization involves a
continuous loop reactor which is continuously charged with suitable
quantities of diluent, catalyst system, and polymerizable compounds in any
desirable order. Typically the polymerization will include a higher
alpha-olefin comonomer and optionally hydrogen. Generally the particle
form polymerization is conducted at a temperature in the range of about
50.degree. C. to about 110.degree. C., although higher and lower
temperatures can be used. Polyethylenes of varying molecular weight
distribution can be produced by varying the amount of hydrogen. The
reaction mixture containing polymer can be continuously withdrawn and the
polymer recovered as appropriate, generally by flashing the diluent and
unreacted monomers and drying the resulting polymer.
The following examples serve to show the present invention in detail by way
of illustration and not by way of limitation.
EXAMPLES
The examples demonstrate the effectiveness of the inventive processes in
preparing new cyclopentadienyl-type ligands and metallocene compounds and
the use of such metallocene compounds in catalyst systems.
Example 1
Cyclopentadienyl-type Ligands
cyclopentadienyl-type ligands were prepared employing Method I by reacting
19 mmol LiCH.sub.2 P(CH.sub.3).sub.2 dissolved in 70 mL tetrahydrofuran
(THF) with 19 mmol fulvene compound dissolved in 25 mL THF at 0.degree. C.
The fulvene solution was added dropwise over a period of 30 to 90 minutes.
The reaction mixture was stirred for 90 minutes at 0.degree. C. The
solvent was removed under vacuum and the residue was hydrolyzed with
aqueous NH.sub.4 Cl solution and extracted with 2.times.30 mL pentane. The
extract was filtered over anhydrous Na.sub.2 SO.sub.4 and dried under
vacuum. The fulvene compounds employed, the resulting
cyclopentadienyl-type ligands, and the respective yields are indicated
below:
6 -phenylfulvene was employed in preparing
[1-phenyl-2-(dimethylphosphino)ethyl]cyclopentadiene and produced 72.9%
yield of orange oil;
6,6-dimethylfulvene was employed in preparing
[1,1-dimethyl-2-(dimethylphosphino)ethyl]cyclopentadiene and produced a
yield of 36.0% as a yellow oil;
6,6-diphenylfulvene was employed in preparing
[1,1-diphenyl-2-(dimethylphosphino)ethyl]cyclopentadiene which yielded
35.0% as an orange oil; and
6-tert-butylfulvene was employed in preparing
[1-tert-butyl-2-(dimethylphosphino)ethyl]cyclopentadiene and produced a
63.2% yield as an orange oil.
Example 2
Metallocenes
Metallocene compounds were prepared by reacting the cyclopentadienyl-type
ligands with metal halides. In a typical example, 1.60 g (5.28 mmol)
[1,1-diphenyl-2-(dimethylphosphino)ethyl]cyclopentadiene, prepared as
described in Example 1, dissolved in 60 mL hexane was reacted with 3.30 mL
(5.28 mmol) n-BuLi (1.6 M in hexane). The n-BuLi was added dropwise over a
period of 30 minutes at room temperature. The reaction mixture containing
orange precipitate was stirred until the evolution of butane gas ceased.
The reaction mixture was cooled to -20.degree. C. employing an isopropyl
alcohol-dry ice bath and then 0.87 mL (7.92 mmol) anhydrous TiCl.sub.4 was
added dropwise over 20 minutes. The mixture was stirred for 2 hours at
-20.degree. C. The resulting brown suspension was filtered and washed with
20 mL of hexane. The filtrate was concentrated under vacuum and placed in
a refrigerator. A yellow-green precipitate separated from the mother
liquor (solid I). The brown solid obtained by filtration was washed with
large amounts of toluene and CH.sub.2 Cl.sub.2. The resulting solution was
dried to give a yellow solid (solid II). Solids I and II were combined to
give 0.81 g (1.76 mmol)
[1,1-diphenyl-2-(dimethylphosphino)ethyl]cyclopentadienyltitanium
trichloride for an overall yield of 33.3%. The metallocene compounds
[1-tert-butyl-2-(dimethylphosphino)ethyl]cyclopentadienyltitanium
trichloride,
[1-phenyl-2-(dimethylphosphino)ethyl]cyclopentadienyltitaniumtrichloride,
and [1,1-dimethyl-2-(dimethylphosphino)ethyl]cyclopentadienyltitanium
trichloride were prepared in a similar fashion employing the respective
cyclopentadienyl-type ligands.
Example 3
A cyclopentadienyl-type ligand containing fluorene was prepared as follows
employing Method II. To a solution of 1.2 g LiCH.sub.2 P(CH.sub.3).sub.2
in 50 mL THF was added 3.0 g (bromomethyl)fluorene in 50 mL THF at
-78.degree. C. over a period of one hour. The mixture was stirred an
additional 30 minutes at room temperature. Filtration of the mixture gave
a clear yellow solution.
A fluorene-containing metallocene was prepared by reacting the thus
prepared yellow solution with 7.1 mL n-butyllithium (1.5 M in hexane).
After stirring for 2 hours at room temperature the solvent was removed and
then 30 mL ether was added. Then a solution of 2.5 g ZrCl.sub.4 in 10 mL
ether was added at -78.degree. C. The mixture was stirred for 10 minutes
at -78.degree. C. and one hour at room temperature. Then the ether was
removed and 60 mL hexane was added. The hexane solution was filtered over
Na.sub.2 SO.sub.4. The solvent was removed and the residue was extracted
with 25 mL toluene and the metallocene was crystallized at -78.degree. C.
Example 4
A cyclopentadienyl-type ligand containing fluorene was prepared as follows
employing Method III. In a reaction vessel8.3 g (0.05 mol) fluorene in 150
mL ether was reacted with 31.3 ml (0.05 mol) butyllithium (1.5 M in
hexane) and then with 6.3 mL (0.05 mol) SiMe.sub.3 Cl in 50 mL pentane to
form trimethylsilylfluorene. Then 6.8 g (0.03 mol) of the thus produced
trimethylsilylfluorene was reacted with 18.7 mL (0.03 mol) butyllithium
(1.6 M in hexane) and 8.12 mL (0.13 mol) CH.sub.2 Cl.sub.2 in 100 mL
pentane for two hours at room temperature to form (Me.sub.3
Si)(ClCH.sub.2)Flu, where Me is methyl and Flu is fluorene. The solvent
was removed leaving a yellow residue. Then 2.5 g (0.009 mol) (Me.sub.3
Si)(ClCH.sub.2)Flue in 30 mL THF was reacted with 0.71 g (0.009 mol)
LiCH.sub.2 PMe.sub.2 in 50 mL THF with stirring at -78.degree. C. to form
(Me.sub.3 Si)(Me.sub.2 P(CH.sub.2).sub.2)Flu. The (Me.sub.3
Si)(ClCH.sub.2)Flu was added over a period of two hours and the reaction
was allowed to continue an additional three hours at -78.degree. C. and
then overnight at room temperature. The solvent was removed and the hexane
gave 1.35 g of dark yellow oily product.
The fluorene-containing metallocene was prepared by reacting 1.35 g (0.004
mol)(Me.sub.3 Si)(Me.sub.2 P(CH.sub.2).sub.2)Flu in 50 mL hexane with 3.5
mL (0.006 mol) butyllithium (1.5 M in hexane) and 1.1 g (0.004 mol)
ZrCl.sub.4 in 10 mL hexane. The ZrCl.sub.4 was added over a period of 2
hours at -78.degree. C. and then stirred for an additional hour at
25.degree. C. The reaction mixture was filtered over Na.sub.2 SO.sub.4.
The solvent was removed and a yellow-brown fine powder was obtained.
Example 5
Polymerizations
Several catalyst systems were employed in the polymerization of ethylene.
The conditions included a total pressure of 450 psig, a partial pressure
of H.sub.2 of 10 psig, and a temperature of 90.degree. C. The
polymerization was conducted in 2 liters isobutane diluent for one hour.
The catalyst systems employed in Runs 101-104 were prepared by contacting
10 mL MAO from Shering with 0.003-0.005 g of each metallocene. The
metallocene
[1,1-dimethyl-2-(dimethylphosphino)ethyl]cyclopentadienyltitanium
trichloride was employed in Runs 101 and 102. The metallocene
[1,1-diphenyl-2-(dimethylphosphino)ethyl]cyclopentadienyltitanium
trichloride was employed in Runs 103 and 104. The polymerizations in Runs
101-104 were conducted employing 3.0 mL of each catalyst system.
The catalyst system in Run 105 was prepared by contacting 9.38 mL MAO from
Ethyl, 0.62 mL toluene and 0.0123 g of the metallocene
[1,1-dimethyl-2-(dimethylphosphino)ethyl]cyclopentadienylzirconium
trichloride.
The results are tabulated in the Table below. Al/M is the moles
aluminum/mole transition metal employed. Methylaluminoxane was employed as
the cocatalyst. Hexene is the grams hexene-1 employed as comonomer.
Productivity is the g polyethylene/g transition metal.circle-solid.hour.
MI is the melt index in g/10 min. run according to ASTM 1238. Density is
g/cc measured according to ASTM
TABLE
______________________________________
Productivity
MI
Metal- Hexene
g PE/g g/10 Density
Run locene A1/M grams M .multidot. hr
min. g/cc
______________________________________
101 A* 730 0 19,000 0.001 0.9714
102 A* 730 50 13,000 0 0.9791
103 B* 1000 0 8,000 0 0.9653
104 B* 1000 50 6,500 0 0.9763
105 C* 470 0 364,000 1.91 0.9688
______________________________________
*A is [1,1dimethyl-2-(dimethylphosphino)ethyl]cyclopentadienyltitanium
trichloride
*B is [1,1diphenyl-2-(dimethylphosphino)ethyl]cyclopentadienyltitanium
trichloride
*C is [1,1dimethyl-2-(dimethylphosphino)ethyl]cyclopentadienylzirconium
trichloride
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